Anthracene dyes and process of making same.



UNITED STATS PATENT OSCAR BELLY, "OF IANNHEYM, "GERMANY, ESSIGNOR T0 BAIDISCH-E ANILIN & 8611A FABRIK, OF LUDWIGSHAI'EN-ON-THE RHINE, GERMANY,A CORPORATION.

ANTHRACENE DYES AND PROCESS OE Specification of Lettersiatent.

Patented Feb. 3,1914.

No Brewing. Original application *filed March 5, 1910, Serial No.547,414. Divided and this application Serial- No..61-9,10'5.

To all whom it may concern:

Be it known that I, OSCAR BALLY, Ph. D., chemist, citizen of the SwissRepublic, residing at Mannheim, Germany, have invented certain new anduseful Improvements in Anthracene Dyes and Processesof Making Same,which invention is divided out of my application for Letters Patentfiled March 5, 1910, Serial No. 547,414, and of which the following is aspecification.

This invention relates to the production of coloring matters of theanthracene series and is divided out of my application for patent SerialNo. 547,414, filed .March 5, 1910.

I have discovered new condensation products of the anthracene series ofthe'type indicated by the general formula in which A, represents asubstituted anthraquinone residue containing only one carbonyl groupintact, such for instance as benzanthrone, anthrapyridone, and the like,X represents a substituent which efi'ects the union ofthe anthraquinoneresidue with the or an anthrapyridone derivative or' the like,

which contains one or more than one substituted group or atom, forinstance chlorin, to -react upon a thiophenol-carboxylic acid body orupon an amino-aryl-carboxylic acid body Among thethiophenolcarboXyl-icacid bodies and the amino-aryl-carboxylic acidbodies which can be used accordin to my invention I includethiophenol-car oxylic acids themselves, amino-aryl-carboxylic acidsthemselves, or a derivative of any one of these com ounds, for instancea salt or ester thereo If the above mentioned thiophenol-carboxylicacids or amino-arylcarboxylic acids be used in the free state for thecondensation, the carboxyl group is liable to be split off to a certainextent, and

to this extent uncarboxylated compounds are obtained, but when 'thesalts are-used inthis condensation, the desired carboxylatedcondensation com-pounds'are obtained smoothly. When --preparing the newcondensation compounds --acco'rding to this invention from halogenatedbenzanthrones or anthrapyridones containing more than one proportionofhalogen, it is ,possible, first, to replace a portion ofthe' halogenusing one of the thicphenol-carboxylic acid compounds or of theamino-aryl-carboxylic acid compounds, and then to replace a furtherportion with the same or a different thiophenol-carboxylic acid compoundor aminoaryl-carboxylic acid compound, so that in this way mixedcondensation products can be vobtained. The condensation can beefl'ected with or without the addition of a substance which actscatalytically.

On treating those new condensation products which contain a carboxylgroupin the ortho position to the sulfur atom or to the iminogroupwith'a'condensing agent, such for instance as sulfuric acid, fumingsulfuric acid, chlorsulfonic acid, phosphoric anhy'd-rid, aluminumchlorid, and 'zinc chlorid, either in the presence or absence of asuitable diluting agent, new coloring matters can be obtained of aconstitution corresponding to the general formula verted into theirsulfonic acid derivatives.

The unsulfonated products are capable of use as vat coloring matters,yielding from red to violet shades of excellent fast-ness, They areinsoluble in water and in dilute acids and alkalis, but are soluble inconcentrated sulfuric acid yielding from brown to violet solutions.

The following examples will serve to illustrate the manner in which thenew condensation products and colorin matters can be obtained. The partsare weight.

Example 1: Mix together 100 parts of 1.5- dichlor-benzanthrone, 150parts of potassium anthranilate and 2 parts of copper oxid and 1,500parts of nitrobenzene, and heat the mixture at its boiling point untilno further separation of the condensation product is observable. Allowthe mixture to cool, collect the solid product, wash it with alcohol,and dry it. The method of procedure can further be varied by usingsolvents, or diluents, other than nitrobenzene and instead of copperoxid, other condensation agents which act in a similar way can beemployed.

Example 2: Mix together 100 parts of 1.5- dichlor-benzanthrone, 125parts of thiosalicylic acid, 100 parts of caustic potash, and 2,000parts of absolute alcohol. Boil the mixture till no unchangeddichloranthraquinone is noticeable, allow the mass to cool, collect, byfiltering, the potassiumsalt of the anthraquinone-1.3-bisthiosalicylicacid which is obtained, dissolve in water, and precipitate the newcondensation product in the form of the free acid, by the addition ofhydrochloric acid.

Example 3: Dissolve 1 part of benzanthrone-1.5-bisanthranilic acid(obtainable from 1.5-dichlor-benzanthrone and sodium anthranilate) in 10parts of concentrated sulfuric acid and heat the solution, at about 100C., until the color (which is at first green) has become yellowish red.Then pour the liquid into water and filter oii tlie reaction productwhich separates out in violet flakes.

Example 4: Introduce one part of benzanthrone-1.5-bisthiosalicylic acid(obtainable from 1.5-dichlor-benzanthrone and sodium thiosalicylate)into 5 parts of fuming sulfuric acid, containing 23% of free S0,, whileavoiding as far as possible, a rise in temperature. The solution, whichis at first violet, gradually becomes brown and finally (after standingfor'some time) red. Then pour the reaction liquid into water and filteroff and wash the product which separates out in red flakes.

On treating the product of the foregoing Examples 3 and 4; with asulfonating agent, for instance with warm fuming sulfuric acid, sulfonicacids can be obtained. The sulfonic acid obtained from the product ofExample 4 dyes wool brilliant red shades of great fastness.

In a similar manner, other analogous compounds can be obtained from theother condensation products herinbefore mentioned.

In the following table I give the appearineaiaa ance and properties ofsome of the intermediate condensation products most readily obtainableaccording to my invention Solution in-- A a Condensation 53 2 Productfromof the Glacial Conc. H180 Warm and K-salt. Water acetic cold boricfield. H2504 acid 4-Chlor-2-methy1 Red- Violet Cherry Brown-Cherryanthrapyrldone brown red. red. red. red. +anthranil1c powder.acid.

Brom-benzan- Violet Fuchsin Orange- Orange- Orangepllilronejzianthrapowder. red. yellowi yellow. yellow.

1 loacl N ow what I claim is 1. The process of producing coloring matterof the anthracene series by subjecting to the action of a condensingagent a compound of the type indicated by the general which can beobtained by subjecting to the action ofacondensing agent a compound ofthe type mdicated by the general formula in which A, represents asubstituted anthraquinone residue containing only one carbonyl groupintact, X represents a substituent effooting the union of theanthraquinone residue with the carboxylic acid, and R represents anaromatic residue, while at is a number less than three, which newcoloring matters are insoluble in water and in dilute acids and alkalis,but are soluble in concentrated sulfuric acid yielding from brown toviolet solutions, in the unsulfonated state dye cotton from a vat red toviolet shades of excellent fastness and which in the sulfonated statecan be employed for dyeing wool.

In testimony whereof I have hereunto set my hand in the presence of twosubscribing witnesses.

OSCAR RALLY. Witnesses:

Ennns'r G. EHRHARDT, A. O. TILLMANN.

Copies ml this patent may be obtained for five cents each, by addressingthe Gommlasioner of Patenta,

Washington, a. e.

